Anthraquinone compounds containing a 2, 2, 2-trifluoroethylamino group



Patented Apr. 5, 1949 ANTHRAQUINON-E COMPOUNDS CONTAIN- ING A 2,2,2TRIFLUOROETHYLAMINO GROUP Joseph B. Dickey, Rochester, N. Y., assignorto Eastman Kodak Company, Rochester, N. Y., a corporation of New JerseyNo Drawing. Application March 26, 1946, Serial No. 657,345

1 Claim. 1 This invention relates to new anthraquinone compounds andtheir application to the art of dyeing or coloring.

The anthraquinone compounds of my invention can be represented by thegeneral formula:

containing 1 to 6, inclusive, carbon atoms, an alkoxyalkylamino groupcontaining 3 to 8, inclusive, carbon atoms and wherein the oxygenlinkage is joined to a carbon atom, other than an a-carbon atom, of thegrouping immediately preceding it, a hydroxyalkylamino group containing2 to 5, inclusive, carbon atoms and wherein there is no hydroxy group onthe carbon atom which is attached to the nitrogen atom, and amonohydroxyalkoxyalkylamino group containing 4 to 9, inclusive, carbonatoms wherein the hydroxy group is attached to a carbon atom, other thanan a-carbon atom, of the alkoxy group furthest removed from the aminogroup, wherein the OCnH2nand CnH2ngroupings present in themonohydroxyalkoxyalkylamino group contain at least two but no more thanthree carbon atoms and wherein the oxygen 1inkage present is joined to acarbon atom, other than an u-carbon atom, of the grouping immediatelypreceding it.

It is an object of my invention to provide new anthraquinone compounds.Another object is to provide a satisfactory process for preparing thenew anthraquinone compounds of the invention. A further object is toprovide colored materials of good fastness properties. A specific objectis to provide colored cellulose acetate textile materials of goodfastness properties. A still further object is to provide a satisfactoryprocess for coloring nylon and organic derivatives of cellulose textilematerials with the new anthraquinone compounds of the invention.

The new anthraquinone compounds of my invention constitute valuable dyesfor the coloration of organic derivatives of cellulose and nylonmaterials, especially textile materials made of these materials. They.are particularly adapted for the coloration of cellulose acetate textilematerials. They possess good afiinity for the aforesaid textilematerials, are readily applied thereto, and yield dyeings thereon whichare of superior gas and light fastness properties. In some instancesdyeings are obtained, for example, on cellulose acetate textilematerials, which possess exceptional gas and light fastness properties.To illustrate, 1-2,2,2-trifiuoroethylamino-4-hydroxyanthraquinone whenapplied directly to a cellulose acetate textile material from an aqueoussuspension of the dye gave a reddish-pink dyeing which, so far as we areaware, is at least twice as fast to light as any dyeing obtained with adye of comparable color applied directly to cellulose acetate from awater bath. The dyeing obtained was also very stable to gas fading.

Orange, reddish-pink, reddish-violet, violet and reddish-blue dyeingsare obtained with the 2,2,2- trifluoroethylaminoanthraquinone compoundsof my invention. The dyeings obtained are more reddish than thoseobtained with the corresponding anthraquinone compounds containing theethylamino group instead of the 2,2,2-trifluoroethylamino group. Thuswhile l-hydroxyl- 2,2,2-trifluoroethylaminoanthraquinone dyes celluloseacetate a reddish-pink color (about the same as that obtained withl-hydroxy-l-aminoanthraquinone) 1-hydroxy-4-ethylaminoanthraquinone dyescellulose acetate a bluish-violet color. Further the dyeing obtained oncellulose acetate with a 25% by weight of a dye mixture of1-hydroxy-4-2,2,2-trifiuoroethylaminoanthraquinone showed little fadingafter a hour light f'astness test (American Association of TextileChemists and Colorists) and very little fading to gas even after 3 timesthe normal AATCC test Whereas a similar dyeing on cellulose acetate withl-hydroxy-4 ethylaminoanthraquinone shows considerable fading after a 24hour light fastness test and considerable fading to gas after the AATCCtest for gas fastness.

Illustrative alkylamino groups include, for example the methylaminogroup, the ethylamino group, the n-propylamino group, the isopropylaminogroup, the n-butylamino group, the n-amylamino group and then-hexylamino group. Illustrative alkoxyalkylamino roups include, forexample, the ,B-methoxyethyl-amino group, the p-ethoxyethylamino group,the fi-(n-propoxwethylamino group, the [i- (n-butoxy) -ethy1amino group,the v-methoxy-(n-propyl)-amino group, the 8- (fl-methoxyethoxy)-ethylamino group the fi-(p-ethoxyethoxy) -ethylamino group, the 8m (/3methoxyethoxy) ethoxy] ethylamino group H [TNTCHHOHZQ CHgCHzO OHaGHZOCH5] the group p [,6- (p-ethoxyethoxy) -ethoxy] -ethy1amino [-f-cmcmoOHZCHQQ 11201120 mm] the ,B- (p-n-butoxyethoxy) -ethy1amino group [1IcH2oH;0 0112011 0 cmcmcflzcm] the 'y- ('y-methoxypropoxy) -prop1yaminogroup Lfi-omomomo cmon cmo 0113] and the p- (p-ethoxypropoxy)-propy1amino. ,group the l-methylol-n-propylamino group the 3-methylol-2-buty1amino group nd-cmon H; the 3-hydroxy-2 -buty1aminogroup CHOH the 4 -hydroxybutylamino 4 the 2-methy1o1-2-buty1amino groupNCCH:OH

and; the 2 -'ethy1o1,-2 -propylamino :group (p -hydroxyethoxy)-ethy1amino [Bi-[ 8 -fi hydroxyethoxy) -ethoxy] -ethy1amino 7y-(y-hydroxypropoxy) -pr0py1amino H [NCH2CH2OCH2CHGH3] and 3 [p-(fi-hydroxy-propoxy) -propoxy] -proareiiillustrative :of: themonohydroxyalkoxyalkylthe dimethylolmethylamino group CH OH- the1,1-dimethy1olethylamino group the l,1-dimethy1o1-n-propylamino groupcmoH- the trimethylolmethylamino group .CHZ 0-H? H NOCH2OH aminogroupsthat can be present in the anthra- -quinone compounds of my invention.

"l-Thexcompounds of my invention can be prezpare'd .in .a variety ofways. 1-2,2,2-trifiuoro- :ethylaminoanthraquinone can be .prepared, vfor example, .by reacting? lenitroanthraquinone withA2,2;2+trifiuoroethylaminein the presence of an inert solvent such asdry pyridine, ethanol or anthraquinone can be prepared, for eXample, byreacting l-aminoA-nitroanthraquinone with:21,2,2-strifiuoroethy1amineinthe presence of pyri- :dine.:anthraquinone can-' be prepared, for example, by vreacting bromine1(10%excess) with 12,2,2-trivfiuor0ethylaminoanthraqminone in the presence ofaninert diluent-.or-solvent such as pyridine, ethanol .or n-butanol. Theuse of pyridine is advantageous. 1--2,2,2 trifluoroethylamino --4-ichloroanthraquinone can be prepared ina simi- JarHmannerby reactingchlorine with 1-2,2;2- Itrifluoroethylaminoanthraquinone. The ch10-rination reaction can also be carried out with -sulfuryl chloride 'anda'catalyst such as ferric .chloride in :an-inertdiluent medium such aspyridine.

1t-f2,'2;2 trifluoroethylaminm l-hydroxyanthraquinone 'can=be preparedby reaetingleuco quinizarin or a mixture-of qu'iniza'rin and leuco quin.izarin with a slight excess of -2,2,2-trifluor0- -ethy-1amine over thattheoretically required --to :replacezone oflthe hydrox-ygroups,

= Compounds wherein-an nalkylamino, alkoxyralkylamino, a"hydroxyalkylamino or a--monohydroxyalkoxyalkylamino group is present inthe 4-position can be prepared by reacting the leuco form of1-2,2,2-trifiuoroethylamino-4-hydroxyanthraquinone with an alkylamine,an alkoxyalkylamine, a hydroxyalkylamine and amonohydroxyalkoxyalkylamine, respectively. These compounds can also beprepared by reacting a leuco l-(alkyl, hydroxyalkyl, alkoxyalkyl orhydroxyalkoxyalkyl) amino 4 hydroxyanthraquinone with2,2,2-trifluoroethylamine. Also mixtures of dyes can be prepared byreacting leuco quinizarin or a mixture of leuco quinizarin andquinizarin with 2,2,2-trifluoroethylamine and one or more aminesselected from the group consisting of an alkylamine, analkoxyalkylamine, a hydroxyalkylamine and a hydroxyalkoxyalkylamine.Where the leuco form of the dye compound is obtained, the leuco dyecompound is oxidized to its nonleuco form by treatment with an oxidizingagent such as air, oxygen, sodium perborate, nitrobenzene, hydrogenperoxide or ammonium persulfate, for example. Normally, the condensationreactions referred to in this paragraph are carried out in the presenceof an inert diluent, which may also act as a solvent, such as water,pyridine, ethanol, n-propanol and n-butanol.

Anthraquinone compounds containing a 2,2,2- trifiuoroethylamino group inboth the 1 and 4 positions can be prepared by methods similar to thosedescribed above. Thus 1,4-di-2,2,2-trifiuoroethylarninoanthraquinone canbe prepared by reacting two molecular equivalent weights of2,2,2-trifiuoroethylamine with 1 molecular equivalent weight of leucoquinizarin or an equivalent amount of a mixture of quinizarin and leucoquinizarin. Any unoxidized dye compound present in the reaction mixtureis oxidized to its nonleuco form. 1 2,2,2-trifluoroethlamino-4-2,2-difluoroethylaminoanthraquinone can be prepared, forexample, by reacting leuco 1-2,2,2-trifiuoroethylamino 4hydroxyanthraquinone with 2,2- difiuoroethylamine and oxidizing theresulting leuco compound formed to its non-leuco form. Sodium perborateor any of the other oxidizing agents indicated herein can be used forthe oxidation.

In those cases where a mixture of quinizarin and leuco quinizarin isused, at least by weight of leuco quinizarin should be present in themixture.

The following examples in which parts are by weight further illustratethe compounds of my invention and their manner of preparation.

Example 1 2.42 parts of leuco quinizarin, 1.09 parts of2,2,2-trifluoroethylamine and 12.2 parts of n-butyl alcohol were placedin a suitable reaction vessel, heated over a hot plate for 14 hours atjust under refluxing conditions, and then heated at refluxing conditionsfor 6 hours. The leuco dye formed was oxidized by adding 3 parts ofWater and 2.31 parts of sodium perborate (NaBO3-4HzO) to the reactionmixture and heating for three hours. The reaction mixture was thenpoured into 500 parts of hot water, with stirring and stirring wascontinued until the reaction mixture was cold, following which thereaction mixture was filtered. The precipitate obtained was washed wellwith water and dried. A good yield of 1-2,2,2-trifiuoroethylamino 4hydroxyanthraquinone was obtained. Upon crystallization from ethylalcohol, the product melted at 143145 C. It gave a wine-red color inacetone and dyed cellulose acetate a reddish-pink color which was excep-Theoretical Found Percent Percent Example 2 2.42 parts of leucoquinizarin, 2.48 parts of 2,2,2-trifluoroethylamine and 8.1 parts ofn-buta- 1101 were placed in a sealed glass tube and heated in a shakingautoclave at 105-120 C. for 12 hours. The wine-red reaction mixture wascooled and removed from the glass tube with the aid of some n-butanolfollowing which the reaction product was oxidized by refluxing gentlywith 5 parts of water and 2.31 parts of sodium perborate for 3 hours.The reaction mixture became somewhat more violet colored upon oxidation.Upon completion of the oxidation reaction, the reaction mixture wascooled and the crystallized product was recovered by filtration. 1.7parts of 1,4-di- 2,2,2-trifiuoroethylaminoanthraquinone were obtained.Upon evaporation of the filtrate, an additional 0.75 part of the productwas obtained. The 2.4-5 parts of crude product thus obtained wererecrystallized from n-butanol to obtain a purified product having amelting point of ZOO-205 C. which gave a violet-pink color in acetoneand which dyed cellulose acetate the same color. The dyeing obtained wasvery fast to light and gas. It dyes nylon a similar color.

Example 3 10 parts of l-nitroanthraquinone in parts of dry pyridine areheated to 100 C. and 5 parts of 2,2,2-trifiuoroethylamine are addeddropwise. A reddish color indicating reaction develops at once and aftera short period of heating, preferably with stirring, the reaction iscomplete. 1-2,2,2.- trifluoroethylaminoanthraquinone crystallizes out ofthe pyridine on cooling and is recovered by filtration. It can befurther purified by recrystallization from a solvent such as pyridine,toluene or acetic acid. The dye compound obtained as described dyescellulose acetate and nylon orange shades. This compound can also beprepared by substituting an equivalent gram molecular weight ofl-chloroanthraquinone or sodium anthraquinone-l-sulfonate forl-nitroanthraquinone in the foregoing reaction.

Example 4 13.4 parts of 1-amino-4-nitroanthraquinone are dissolved in148 parts of dry pyridine and heated on a steam bath. '7 parts of2,2,2-trifluoroethylamine in 250 parts of dry pyridine are then addeddropwise with stirring while heating on the steam bath. The reactionmixture immediately turns to a reddish-violet color. When no furthercolor change takes place, the reaction mixture is allowed to cool and1-2,2,2-trifiuoroethylaminoi-aminoanthraquinone crystallizes out and isrecovered by filtration. The dye compound thus obtained can be purifiedby recrystallization from a solvent such as pyridine, toluene or aceticacid. It colors cellulose acetate and nylon textile materials violetshades.

Example 5 12 parts of leuco quinizarin are dissolved in 122 parts. of;n-butyl alcohol; and; 5. parts; .of; =.2 .2,'2.I

compound obtainedwis purified by crystallization-- from-pyridine. Itcolors cellulose acetate and nylon textile materials violet shadesWhich-possess.

gOOd fastness to light and gas.

Example 6 12 parts of leuco quinizarin are dissolved in122 parts of.n-butyl alcohol and 1.6 parts of-methylamine as a 25% water solution areaddeddrop wiseunder. refluxing conditions. Then 5.5 parts of2,2,2-trifluoroethylamine' in 16.2 parts of n-butyl alcohol are addeddropwise Whilemaintaining the reaction mixture under refluxingconditions. Refluxing is continued foran additional- 10 hours followingwhich the leuco dye compoundformed is obtained bypassing air into.thereaction mixture. If desired, sodium perborate can be used to effectthe oxidation.

separates from the reaction mixture and isrecovered by filtration. Itcan'be-purified by crystal lization from a solvent such as pyridine orn-butyl alcohol. It colors cellulose acetate and nylon textile materialsreddish-blue shades which are of goodfastness to light and gas;

By" the substitution, of an equivalent. molecular weight of ethylaminefor methylami-nein the foregoing example, l-2,2,2etrifluoroethylamino4-ethylaminoanthraquinone is obtained. This dye compound similarlycolors cellulose acetate and-nylon textile materialsreddish-blue shadeswhich are ofgood fastness to: light andgas.

Example 7 12 parts of leuco quinizarin are dissolved iii-1 22' parts ofn-butyl alcohol and parts. of. 2,2;2-trifluoroethylamine are addedthereto and the re.- action mixture is heated to refluxing conditions.When no further color change takes. place, 3.5.

parts of ethanolamine areadded.dropWis ;.With.

stirring to the reaction mixture which is maintained under refluxingconditions. The reaction mixture is refluxed, with stirring, for anadditional hours and then the leuco dye compound formed is oxidized bypassing in air, or de sired, the oxidation can be effected with sodiumperborate. 1-2,2,2-trifiuoroethylaminoi-fi-hy--droxyethylaminoanthraquinone precipitatesfrom the reaction mixture uponcooling and -isrecovered by filtration. It is purified by recrystallization'from pyridine. It colors cellulose acetate and nylon textilematerials reddish-blue shades which are of. good fastness to light andgas.

Example 8 12 parts of leuco quinizarin are dissolved-int 122 parts ofn-butyl alcohol and 5 parts of'2;2,2-'tri-' fiuoroethylamine in 16.2parts of n-butyl alcohol are added dropwise under refluxing conditions.Them: 8 -.parts of 1 fl-methoxyethylamine in 16.2

l.-2,2,2-.tri-' fiuoroethylamino- 4 -methylaminoanthraquinoneparts ofn.-butyl alcohol. are: addedxdropwise with stirring; to: the: reaction;mixture: which .is maintained under refluxing-.conditions- Refiuxingdscontinued for an additional 10 hours. The leuco dyecompound; formed isoxidized and libel-2,2,2-

trifluoroethylamino- 4 efl-methoxyethylaminoanthraquinone.whichrprecipitates from the reaction mixture is recoveredby'flltration; washed with Wateriand'dried. It is. purified byrecrystallizatiorr'from- 'pyridine. It colors cellulose acetate andnylontextilev materials reddish-bluewshades which .aresof goodlfastnessto: light. and :gas; The: oxidation reaction referred to. above can becarried' outlay passing air into thereaotionmixture or: bymeans of: theoxidizing agents specifically mentioned. hereinbefore or; by anyother-suitableoxidizing. agent.

Example. 9 r

12 parts ofileuco quinizarin are dissolved in122' parts. ofin-butylalcohol and 5 parts of 2,2,2-trifiuoroethylamine in 16.2 parts ofn-butyl' alcohol are, added dropwise under. refluxing conditions. Then4.5 parts of ,6-(B-hydroxyethoxy)-ethyl'- amine in. 16.2 partsof'n-butyl alcohol are added dropwise with stirring to the reactionmixture which is maintained under refluxing conditions. Refluxing iscontinued for an. additional ten. hours. The leuco dye compound formedis then oxidized by means of sodium perborate and the.1.-2,2,2-trifiuoroethylaminoi e- (,B-hydroxyethoxy)-ethylaminoanthraquinone which precipitates from. the reaction mixture.is recovered by filtration, washed with water anddried. It is purifiedby recrystallization from pyridine... It

' colors cellulose acetate andv nylontextile. materialsreddish-blue.shades which. are. of. good fastnessto light andgas.

Example 10 6 'parts of leucoquinizarin; G-parts of quinizarin, :4'partsof 'ethylamine and-6 parts of'2,2,2; trifluoroethylamine are reacted in122 parts of n-butyl alcohol at 100 C. with stirring for 15 hours. Thereaction mixture'is worked up. in accordance with the proceduredescribed in Ex amp1e".9.. An intimate mixture of.1,4-.-diethylamin'oanthraquinone, 1,4-di-2;2,2trifluoroethylaminoanthraquinone and l-2,2;2- trifluoroethyl-=amino-4-ethylaminoanthraquinone isobtained.

Frequently, dye mixtures having improved dyeingcharacteristics: can beobtained in the manner justzindicated. Asis apparent, a widevariety ofamines can be used- Thus. mixtures of methylamine and2,2,2-trifluoroethylamine; n-propylamine and 2,2,2 trifluoroethylarnine;ethanolamine and 2,2,2-trifiuoroethylamine; p-ethoxyethylamine and'2.2,2-trifluoroethylamine, methylamine. ethylamineand2,2,2-trifluoroethyl amine and 2,2-difiuoroethylamine and 2,2,2-tri--fiuoroethylamine, for example, can be employed.

Example 11:

61 parts of 1-2,2,2-trifluoro.ethylaminoanthraquinone are dissolved in590 parts ofpyridineand heated on a water bath to C. While stirring.Then .while maintaining. this temperature, 33.2 parts of bromine areadded. to. the reaction mixture over a 1 /2 hour period. The reactionmixture is then slowly heated to -95 0., maintained at this temperaturefor two hours and the 1-2;2,2etrifluoroethylamino 4 bromoanthraequinonewhich is formed is recovered. by filtration; WashedwithlOO-partsof pyridine and dried; The dye compound thusobtained'colors cellulose acetate and nylon textile materials orangeshades. The following compounds further illustrate the compoundsincluded within the scope of my invention. They can be prepared by themethods described hereinbefore.

- 2, 2-trifluoroethy1amino-4-chloroanthraquinoue2-trifluoroethylamino-4n-propylaminoanthraquinoue-trifluoroethylamiuo-4-isopropylaminoanthraquinonetrifluoroethylaminokn-butylaminoanthraquinone-trifluoroethy1amin0-4-11-amylaminoanthraquiuone-trifluoroethylaminoi-n-hexylaminoanthraquinouetrifluoroethylamino-4-'y-hydroxy'propylamiuo-anthraquinonetrifluoroethylamin-4-w-hydroxyamylamiuo-anthraquinonep-(p-hydroxyethoxy) -ethylamine, c [,6 (/3 hydroxyethoxy) -ethoxyl-ethylamine, 48 (B -hy droxypropoxy) propylamine,c-lp-(p-hydroxypropoxy) -propoxyl -propy1amine, 'y('y-hyd1OXypropoxy)propylamine, 'y-( -methoxypropoxy) propylamine, -ethoxypropoxy)-propylamine 3 with ammonia in the presence of Raney nickel inaccordance with the procedure described in my U. S. Patent 2,357,176.

While the dye compounds of my invention have been described moreparticularly in connection with the coloration of cellulose acetate andnylon textile materials it is to be noted that they are useful for thecoloration of the other materials named herein and that they yield aboutthe same colors on these materials as they do on cellulose acetate andnylon.

Typical organic derivatives of cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such as celluloseacetate, cellulose formate, cellulose propionate, or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organic acid estersof cellulose such as cellulose acetate-propionate, celluloseacetate-butyrate, and the cellulose ethers such as methyl cellulose,ethyl cellulose, or benzyl cellulose.

The anthraquinone dye compounds of my invention may be advantageouslydirectly applied to the material undergoing coloration in the form of anaqueous suspension which can be prepared by grinding the dye to a pastein the presence of a sulfonated oil, soap or other suitable dispersingagent and dispersing the resulting paste in water. In some instances,the dye may possess sufficient solubility in water as to render the useof a dis- -trifluoroethylamiuo-4- B-hydroxypropylamino-antbraquinone ItrifluoroethylaminoA-B, -dihydroxypropylaminoanthraquinonetrifluoroethylamino-4-(1-methylolethyl)-aminoanthraqumone-trifiuoroethylamino-4-dimethylolmethylaminoanthraquinoue 2trifluoroethylamino-4-triinethylolmethylaminoanthraqumone-trifluoroethylamiuo4-(S-methylol- -butyl)-aminoanthraquinpne-trifiuoroethylamiuo-4-(l, l-dimethylolethyl)-aminoanthraqu1noue-trifluoroethy1amiuo-4-(l, l-dimethylol-n-propyl)-aminoauthraqumone-trifluoroethylamino-4-(l-methylol-n-propyl)-aminoanthraqu1nonetritluoroethylamino-4-(Ti-hydroxy-Z-butyl)-aminoanthraqmnonetrifiuoroethylamino-4-(2methy1o1-2-buty1)-aminoanthraqumone-trifluoroethy1amino-4-(2-ethy1ol-2-propyl)-amiuoanthraqu1nonez-trifluoroethylamino-ifl- (n-propoxyethyl) -aminoanthraquinqne 1-2-trifluoroethylamino-4-y-methoxy-(n-propyl)-amiuoanthraquinono 1-z-trifluoroethylamino-l-fi-fB-methoxyethoxy)-ethylammoanthraqumoue l- 2-10 persing agent unnecessary. Generallyspeaking, however, the use of adispersing agent is desirable. Direct dyeing operations can, withadvantage, be conducted at temperatures of about 60-85" C. but anysuitable temperature may be used. Thus,

fl(fl-cthoxyethoxy)-ethoxy]-ethylaminoa 1thraquinone-trlfluoroethylamiuo-4- fl- B-n-butoxyethoxy) -ethylammqauthraqumone-trifiuoroethylamino-4- -methoxypr0poxy) -propyla1 mnoanthraqmnone-trifluoroethylamino-4-B-(B-ethoxypropoxy) -propylammoanthragu1none-trifluoroethylamiuo-4-B-[ B-( B-hydroxyethoxy)-ethoxy1-etl1y1am1no-trifluoroethylamiuo-4- fl-( B-hydroxypropoxy) -ethylamu1 oanthraqum onez-trifluoroethylamino- B-(B-hydroxypropoxy)-propylammoanthraqu none s2-trifluoroethylamiuo-4- 6-[ B-( B-hydroxypropoxy) property]-propylamnoanthraqumone 2-trifluoroethylamino-4-- -('y-hydroxypropoxy)-propy1ammoanthraqu1none 2-trifluoroethylamino-4-y-[-(-y-hydroxypropoxy)-propoxy]-prop anthraquinone ylaminoanthraquinonethe textile material to be dyed or colored is ordinarily added to thedyebath at a temperature lower than that at which the main portion ofthe dyeing is to be efiected, a temperature approximating 45-55" C., forexample, following which the temperature is raised to that selected forcarrying out the dyeing operation. The temperature at which the dyeingis conducted may, of course, be varied somewhat depending upon theparticular material undergoing coloration. As is understood by thoseskilled in the art, the intensity of dyeing can be varied by varying theproportion of dye to material undergoing coloration. Generally speaking,0.12% by weight of dye to material is employed although any desiredproportions can be used.

Suitable dispersing agents together with the amounts that may beemployed are disclosed in McNally and Dickey U. S. Patent 2,115,030,issued April 26, 1938. The process disclosed in this patent for thedyeing of cellulose acetate can be used in applying the dyes of thepresent invention to organic derivatives of cellulose and nylon textilematerials.

In order that my invention may be entirely clear, it is here noted thatthe alkylamino, alkoxyalkylamino, hydroxyalkylamino andmonohydroxyalkoxyalkylamino groups are conveniently introduced into theanthraquinone nucleus by means of the corresponding primary amine inaccordance with the procedure described hereinbefore. To illustrate, thetrimethylolmethylamino and p-hydroxyethylamino groups, for example, canbe introduced by means of trimethylolmethylamine and ethanolamine,respectively.

While pyridine, n-butyl alcohol, ethyl alcohol, toluene and acetic acidhave been disclosed as solvents which can be used to purify thecompounds of my invention, chloroform and nitrobenzene can also be used.The purification can be affected by adding the compound to be purifiedto the solvent, heating to effect solution of the compound and thencooling to effect precipitation of the compound. Alternately, thecompound can be added to the heated solvent. As the methods ofpurification are well known to those skilled

